The present invention relates to a solid formulation of a crop protection product with delayed release of the active ingredient, obtainable by preparing a melt comprising:
0.1-80% by wt. of an active ingredient which can be used in crop protection, or of a combination of such active ingredients,
10-80% by wt. of at least one mineral filler,
0-20% by wt. of inorganic or organic additives, and
to 100% by wt. of at least one thermoplastic water-insoluble polymer,
the total of all constituents equaling 100% by weight, and subsequent shaping.
The invention furthermore relates to a process for the preparation of a solid formulation of a crop protection product, which comprises melting at least one active ingredient, at least one mineral filler and, if appropriate, inorganic or organic additives with at least one thermoplastic, water-insoluble polymer (solubility less than 100 mg per 1 of water at 20xc2x0 C.) in an extruder to give a thermoplastic mixture and subsequently subjecting this mixture to shaping, either in the hot or cold state.
The invention furthermore relates to a process which comprises using in solid form such a solid formulation of a crop protection product for controlling phytopathogenic fungi, undesired vegetation, undesired attack by insects or mites, and/or for regulating plant growth, and allowing it to act on plants, their environment or on seed. Such solid formulations furthermore release the active ingredient(s) which it comprises in a controlled and slow manner (complete release within several days up to some months) into the environment (soil, aqueous medium, plants). This leads to a biological availability over a prolonged period to suit the respective purpose. For example, this is necessary for active ingredients which are insufficiently persistent in soil and/or plant, for active ingredients which are phytotoxic to the crop plant, or else for applications where it is required that the availability or release of active ingredient extends over a prolonged period.
Formulations comprising active ingredient which are prepared by melt extrusion are generally known. Extruding and subsequent shaping of melts of water-soluble polymers, preferably copolymers of vinylpyrrolidone, which contain active ingredient are described in EP-A 240904 and EP-A 240906.
WO 94/08455 describes the coextrusion of crop protection products with polyvinylpyrrolidone and subsequent cooling, crushing and grinding. The ground extrudate disperses rapidly and finely in water and is suitable for spray applications.
There are furthermore known solid formulations of crop protection products which are prepared by melt extrusion with subsequent shaping and which allow a controlled, slow release of pesticides.
WO 91/03940 describes biodegradable pesticide-comprising matrices, their preparation by means of melt extrusion with subsequent shaping, and their use for the controlled release of pesticides. In addition to synthetic polymers ( less than 25%, mainly ethylene/vinyl acetate copolymers), starch and starch derivatives are subjected to melt extrusion together with the respective active substances (carbosulfan inter alia) with addition of water and glycerol to give the matrix. Depending on the formula, the matrices release the active ingredients in water within weeks or months.
WO 95/28835 describes the preparation of agrochemical formulations with hydrophobic and hydrophilic waxes. Active ingredient, carnauba wax and polyethylene glycol are subjected to melt extrusion, ground and graded. The 500-1000 xcexcm fraction is released in water. Depending on the composition, 14-100% of the active ingredients are released after 10 hours.
U.S. Pat. No. 5,643,590 describes insecticidal compositions whose mammalian toxicity is markedly reduced. In a multi-step process, pesticides together with PVC, stabilizer, plasticizer and mineral additive are mixed intimately at 75-110xc2x0 C., and the mixture is cooled to 70xc2x0 C., transferred into an extruder, extruded at 150-180xc2x0 C. and subsequently pelleted. The pellets, which do not dust, exhibit a markedly reduced toxicity to mammals and a prolonged activity (100% worm control over 10 weeks).
DE 19 622 355 describes the preparation by melt extrusion and injection molding of shaped articles which exhibit controlled release. The crop protection agentxe2x80x94together with a vinyl acetate polymer which is insoluble in water and a water-soluble polymer (polyvinyl acetate/vinylpyrrolidone)xe2x80x94is subjected to melt extrusion and granulation.
Formulations based on synthetic polymers and starch (WO 91/03940) can be plastified homogeneously and granulated to give dust-free granules in a simple mannerxe2x80x94i.e., inter alia, without addition of water and/or glycerolxe2x80x94only if the polymer content is high ( greater than 60%) and rapidly show signs of decomposition since the starch is sensitive to heat and shearing forces. Also, such formulations swell and exhibit low density and thus only show insufficient sedimentation in water or soils flooded with water.
While formulations based on hydrophobic and hydrophilic waxes (WO 95/28835) are easy to prepare by simply melting them together with the active ingredient, they are not easy to process (for example extrusion granulation, hot cutting) and are not dimensionally stable upon heat aging (14 days at 54xc2x0 C.) as a result of the wax-like consistency. Moreover, formulations made of stearic acid or stearyl alcohol and PEG do not sediment in water (density less than 1 g/ml).
U.S. Pat. No. 5,643,590 describes a complicated multi-step process in which pesticides are mixed intimately at 75-110xc2x0 C. with PVC, stabilizer, plasticizer and mineral additive, the mixture is cooled to 70xc2x0 C., transferred into an extruder and extruded at 150-180xc2x0 C., and the extrudate is subsequently pelleted. The lack of thermal stability of a large number of active ingredients does not allow high temperature stress because of the danger of decomposition. Moreover, the manufacturing process should be as simple as possible.
In DE 19 622 355, crop protection agents are subjected to melt extrusion and granulation together with a vinyl acetate polymer which is insoluble in water and a water-soluble polymer (polyvinyl acetate/vinylpyrrolidone). Due to low glass transition temperatures, formulations based on polyvinyl acetate polymers exhibit insufficient heat resistance. Upon heat aging (14 days at 54xc2x0 C.), granulated melt extrudates made of polyvinyl acetate and polyvinylpyrrolidone coalesce to form a coherent mass.
The problems are insufficient heat and storage stability, inadequate sedimentation, poor granulation properties, inadequate homogeneity of the melt, and complicated and expensive production.
It is an object of the present invention to provide a solid, storage-stable, slow-releasing crop protection formulation which settles in water, can be granulated and can be prepared readily from inexpensive components by subjecting a mixture of solids to melt extrusion, followed by shaping.
We have found that this object is achieved by the composition described at the outset and the process for its preparation.
In general, suitable active ingredients are those which do not undergo decomposition under the processing temperatures when preparing the melt. Preferred substances are those which are solid at room temperature since these are easier to mix and meter. However, the use is not restricted to solid active ingredients since even liquid active ingredients can be processed by means of a solid matrix to give a solid, heat-resistant and storage-stable formulation.
The amount of active ingredient components in the total formulation may vary within wide limits, depending on efficacy, release rate and processability. Thus, the active ingredient content may range from 0.1-80% by weight, preferably from 0.5-40% by weight, especially preferably from 1-20% by weight, based on the total formulation. The only condition is that the formulation is still thermoplastically processable.
Crop protection agents which may be mentioned are fungicides, herbicides, insecticides and growth regulators. Combinations are also possible.
The following list of herbicides identifies possible active ingredients, but is not to be understood as being restricted to these.
b1 1,3,4-Thiadiazoles:
buthidazole, cyprazole
b2 Amides:
allidochlor (CDAA), benzoylprop-ethyl, bromobutide, chlorthiamid, dimepiperate, dimethenamid, s-dimethenamid, diphenamid, etobenzanid (benzchlomet), flamprop-methyl, fluthiamide, fosamin, isoxaben, monalide, naptalame, pronamid (propyzamid), propanil
b3 Aminophosphoric acids:
bilanafos, (bialaphos), buminafos, glufosinate-ammonium, glyphosate, sulfosate
b4 Aminotriazoles:
amitrol
b5 Anilides:
anilofos, mefenacet
b6 Aryloxyalkanoic acid [sic]:
2,4-D, 2,4-DB, clomeprop, dichlorprop, dichlorprop-p, dichlorprop-p (2,4-DP-P), fenoprop (2,4,5-TP), fluoroxypyr, MCPA, MCPB, mecoprop, mecoprop-P, napropamide, napropanilide, triclopyr, N-(1-cyano-1,2-dimethylpropyl)-2-(2,4-dichloro-phenoxy)propionamides [sic]
b7 Benzoic acids:
chloramben, dicamba
b8 Benzothiadiazinones:
bentazone
b9 Bleachers:
clomazone (dimethazone), diflufenican, fluorochloridone, flupoxam, fluridone, pyrazolate, sulcotrione (chlormesulone), isoxaflutole, isoxachlortole, mesotrione
b10 Carbamates:
asulam, barban, butylate, carbetamid, chlorbufam, chlorpropham, cycloate, desmedipham, di-allate, EPTC, esprocarb, molinate, orbencarb, pebulate, phenisopham, phenmedipham, propham, prosulfocarb, pyributicarb, sulf-allate (CDEC), terbucarb, thiobencarb (benthiocarb), tiocarbazil, tri-allate, vernolate
b11 Quinoline [sic] acids:.
quinclorac, quinmerac
b12 Chloroacetanilides:
acetochlor, alachlor, butachlor, butenachlor, diethatyl ethyl, dimethachlor, metazachlor, metolachlor, pretilachlor, propachlor, prynachlor, terbuchlor, thenylchlor, xylachlor, s-metolachlor
b13 Cyclohexenones:
alloxydim, tepraloxydim, clethodim, cloproxydim, cycloxydim, sethoxydim, tralkoxydim, 2-{1-[2-(4-chlorophenoxy)-propyloxyimino]butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2- cyclohexen-1-one, butroxydim, clefoxydim
b14 Dichloropropionic acids:
dalapon
b15 Dihydrobenzofurans:
ethofumesate
b16 Dihydrofuran-3-ones:
flurtamone
b17 Dinitroanilines:
benefin, butralin, dinitramin, ethalfluralin, fluchloralin, isopropalin, nitralin, oryzalin, pendimethalin, prodiamine, profluralin, trifluralin
b18 Dinitrophenols:
bromofenoxim, dinoseb, dinoseb-acetate, dinoterb, DNOC
b19 Diphenyl ethers:
acifluorfen-sodium, aclonifen, bifenox, chlornitrofen (CNP), difenoxuron, ethoxyfen, fluorodifen, fluoroglycofen-ethyl, fomesafen, furyloxyfen, lactofen, nitrofen, nitrofluorfen, oxyfluorfen
b20 Dipyridylenes:
cyperquat, difenzoquat-methylsulfate, diquat, paraquat dichloride
b21 Ureas:
benzthiazuron, buturon, chlorbromuron, chloroxuron, chlortoluron, cumyluron, dibenzyluron, cycluron, dimefuron, diuron, dymron, ethidimuron, fenuron, fluormeturon, isoproturon, isouron, karbutilate, linuron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, monuron, neburon, siduron, tebuthiuron, trimeturon
b22 Imidazoles:
isocarbamide
b23 Imidazolinones:
imazamethapyr, imazapyr, imazaquin, imazethabenz-methyl (imazame), imazethapyr, imazapic
b24 Oxadiazoles:
methazole, oxadiargyl, oxadiazon
b25 Oxiranes:
tridiphane
b26 Phenols:
bromoxynil, ioxynil
b27 Phenoxyphenoxypropionic esters:
clodinafop, cloquintocet, cyhalofop-butyl, diclofop-methyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, fenthiapropethyl, fluazifop-butyl, fluazifop-p-butyl, haloxyfop-ethoxyethyl, haloxyfop-methyl, haloxyfop-p-methyl, isoxapyrifop, propaquizafop, quizalofop-ethyl, quizalofop-p-ethyl, quizalofop-tefuryl
b28 Phenylacetic acids:
chlorfenac (fenac)
b29 Phenylpropionic acids:
chlorophenprop-methyl
b30 Protoporphyrinogen IX oxydase inhibitors:
benzofenap, cinidon-ethyl, flumiclorac-pentyl, flumioxazin, flumipropyn, flupropacil, fluthiacet-methyl, pyrazoxyfen, sulfentrazone, thidiazimin, carfentrazone
b31 Pyrazoles:
nipyraclofen, ET 751
b32 Pyridazines:
chloridazon, maleic hydrazide, norflurazon, pyridate
b33 Pyridinecarboxylic acids:
clopyralid, dithiopyr, picloram, thiazopyr, diflufenzopyr
b34 Pyrimidyl ethers:
pyrithiobac-acid, pyrithiobac-sodium, KIH-2023, KIH-6127, pyribenzoxym
b35 Sulfonamides:
flumetsulam, metosulam
b36 Sulfonylureas:
amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron methyl, ethoxysulfuron, flazasulfuron, halosulfuron-methyl, imazosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl, N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]amino]carbonyl]-2-(trifluoromethyl)benzene sulfonamide, sulfosulfuron, idosulfuron
b37 Triazines:
ametryn, atrazine, aziprotryn, cyanazine, cyprazine, desmetryn, dimethamethryn, dipropetryn, eglinazine-ethyl, hexazinon, procyazine, prometon, prometryn, propazine, secbumeton, simazine, simetryn, terbumeton, terbutryn, terbutylazine [sic], trietazine
b38 Triazinones:
ethiozin, metamitron, metribuzin
b39 Triazolecarboxamides:
triazofenamid
b40 Uracils:
bromacil, lenacil, terbacil
b41 Various:
benazolin, benfuresate, bensulide, benzofluor, butamifos, cafenstrole, chlorthal-dimethyl (DCPA), cinmethylin, dichlobenil, endothall, fluorbentranil, mefluidide, perfluidone, piperophos, flucabazone, oxaciclomefone (MY 100)
The following list of compounds which have growth-regulatory activity identifies possible active ingredients from this group but is not to be understood as being restricted to these.
Compounds with growth-regulatory activity, such as
1-naphthylacetamide, 1-naphthylacetic acid, 2-naphthyloxyacetic acid, 3-CPA, 4-CPA, ancymidol, anthraquinone, BAP, butifos; tribufos, butralin, chlorflurenol, chlormequat, clofencet, cyclanilide, daminozide, dicamba, dikegulac sodium, dimethipin, chlorfenethol, etacelasil, ethephon, ethychlozate, fenoprop, 2,4,5-TP, fluoridamid, flurprimidol, flutriafol, gibberellic acid, gibberillin [sic], guazatine, imazalil, indolylbutyric acid, indolylacetic acid, karetazan, kinetin, lactidichlor-ethyl, maleic hydrazide, mefluidide, mepiquat-chloride, naptalam, paclobutrazole, prohexadione calcium, quinmerac, sintofen, tetcyclacis, thidiazuron, triiodobezoic [sic] acid, triapenthenol, triazethan, tribufos, trinexapacethyl, uniconazole.
The following list of insecticides identifies possible active ingredients, but is not to be understood as being restricted to these.
Neonicotinoids/chloronicotinyl compounds:
imidacloprid, acetamiprid, nitenpyram, thiacloprid, thiamethoxam, MIT-446
organophosphates such as
acephate, azinphos-methyl, chlorpyrifos, dimethoate, disulfoton fosthiazate, methamidophos, methidathion, methyl-parathion, oxydemeton-methyl, phorate, phosalone,
phosmet, profenofos, trichlorfon, malathion, phosphamidon, monocrotophos, fenitrothion, diazinon, EPN
carbamates such as
alanycarb, aldicarb, benfuracarb, carbofuran, carbosulfan, furathiocarb, methomyl, oxamyl, pirimicarb, thiodicarb, fenobucarb
pyrethroids such as
bifenthrin, cyfluthrin, cypermethrin, deltamethrin, esfenvalerate,
fenpropathrin, lambda-cyhalothrin, permethrin, tau-fluvalinate, tralomethrin, zeta-cypermethrin
urea derivatives such as
diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron,
novaluron, triflumuron
juvenuids [sic] such as
buprofezin, diofenolan, fenoxycarb, pyriproxifen, methoxyfenozide, tebufenozide
Various such as
abamectin, spinosad, amitraz, cartap, chlorfenapyr, diafenthiuron, fipronil, fudioxonil
pyridaben, tebufenpyrad, fenazaquin, fenpyroxymate, thiocyclam, silafluofen
The following may be mentioned as being especially preferred: 
The insecticides of the formulae III to IX are commercially available under the trade names mentioned hereinbelow in brackets:
III: EP-A 192,060, common name: imidacloprid (trade name: Admire(copyright), Gaucho(copyright), Bayer)
IV: common name: acetamiprid (trade name Mospilan(copyright), Nippon Soda)
V: CAS RN 120738-89-8, common name: nitenpyram (trade name: Bestgard(copyright), Takeda Chemicals);
VI: Colliot et al., Proc. Br. Conf. Dis. 1992, 1, 29, common name: fipronil (trade name: Regent(copyright), Rhone-Poulenc);
VII: U.S. Pat. Nos. 3,474,170; 3,474,171 and DE-C 1,493,646; common name: carbofuran (trade name Curaterr(copyright), Bayer; Furadan(copyright), FMC);
VIII: Proc. Br. Crop Prot. Conf., 1979, Vol.2, 557, common name:carbosulfan (trade name: Marshall(copyright), FMC);
IX: FR-A 2,489,329; Proc. Int. Congr. Plant Prot. 10th, 1983, 2, 360, common name: benfuracarb (trade name: Oncol(copyright), Otsuka, Furacon(copyright), Siapa Chem.)
X: CAS RN 111 988-49-9, common name: thiacloprid (developed by Bayer);
XI: CAS RN [131341-86-1], common name: fludioxonil, (trade name: Celest(copyright), Ciba Geigy), 4-(2,2-difluoro-1,3-benzodioxol-7yl)-1H-pyrrole-3-carbonitrile
XII: Tefuranitde (proposed), MTI-466, The 1998 Brighton Conference xe2x80x9cPest and Diseasesxe2x80x9d, Conference Proceedings, Vol 1, page 81
XIII: Thiamethoxam (CGA 293343), The 1998, Brighton Conference xe2x80x9cPest and Diseasesxe2x80x9d, Conference Proceedings, Vol 1, page 27
The following list of fungicides identifies possible active ingredients, but is not to be understood as being restricted to these.
Fungicides from the following classes
sulfur, dithiocarbamates and their derivatives such as iron(III) dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebis(dithiocarbamate), manganese ethylenebis(dithiocarbamate), manganese zinc ethylenediaminebis(dithiocarbamate), tetramethylthiuram disulfides [sic], ammonia complex of zinc N,N-ethylenebis(dithiocarbamate), ammonia complex of zinc N,Nxe2x80x2-propylenebis(dithiocarbamate), zinc N,Nxe2x80x2-propylenebis(dithiocarbamate), N,Nxe2x80x2-polypropylenebis(thiocarbamoyl)disulfide;
nitro derivatives such as dinitro-(1-methylheptyl)phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate, 2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate, diisopropyl 5-nitroisophthalate;
heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethyl phthalimidophosphonothioate, 5-amino-1-[bis(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithiolo[4,5-b]quinoxaline, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate, 2-methoxycarbonylaminobenzimidazole, 2-(2-furyl)benzimidazole, 2-(thiazol-4-yl)benzimidazole, N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide, N-dichlorofluoromethylthio-Nxe2x80x2,Nxe2x80x2-dimethyl-N-phenylsulfamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-mercaptomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, pyridin-2-thiol 1-oxide, 8-hydroxyquinoline and its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine 4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide, 2,4,5-trimethylfuran-3-carboxanilide, N-cyclohexyl-2,5-dimethylfuran-3-carboxamide, N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholin-2,2,2-trichloroethyl acetal, piperazin-1,4-diylbis-1-(2,2,2-trichloroethyl)formamide, 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecylmorpholine and its salts, 2,6-dimethyl-N-cyclododecylmorpholine and its salts, N-[3-(p-tert-butylphenyl)-2-methylpropyl]cis-2,6-dimethyl-morpholine, N-[3-(p-tert-butylphenyl)-2-methylpropyl]piperidine, 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazole, 1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazole, N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-Nxe2x80x2-imidazolylurea, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol, (2RS,3RS)-1-[3-(2-chlorophenyl)-2-(4-fluorophenyl)oxiran-2-ylmethyl]-1H-1,2,4-triazole, a-(2-chlorophenyl)-a-(4-chlorophenyl)-5-pyrimidinemethanol [sic], 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis-(p-chlorophenyl)-3-pyridinemethanol, 1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene, 1,2-bis(3-methoxycarbonyl-2-thioureido)benzene, anilinopyrimidines such as N-(4,6-dimethylpyrimidin-2-yl)aniline, N-[4-methyl-6-(1-propynyl)pyrimidin-2-yl]aniline, N-[4-methyl-6-cyclopropylpyrimidin-2-yl]aniline,
phenylpyrroles such as
4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile,
cinnamamides such as
3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloylmorpholine,
and a variety of fungicides such as dodecylguanidine acetate, 3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutarimide, hexachlorobenzene, DL-methyl N-(2,6-dimethylphenyl)-N-furoyl-(2)-alaninate, DL-N-(2,6-dimethylphenyl)-N-(2xe2x80x2-methoxyacetyl)alanine methyl ester, N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyrolactone, DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)alanine methyl ester, 5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine, 3-[3,5-dichlorophenyl(-5-methyl-5-methoxymethyl)-1,3-oxazolidine-2,4-dione [sic], 3-(3,5-dichlorophenyl)-1-isopropylcarbamoylhydantoin, N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]acetamide, 1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole, 2,4-difluoro-a-(1H-1,2,4-triazolyl-1-methyl)benzhydryl [sic] alcohol, N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine, 1-((bis(4-fluorophenyl)methylsilyl)methyl)-1H-1,2,4-triazole, 2-(4-chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, 3-chloro-4-[4-methyl-2-(1H-1,2,4-triazol-1-ylmethyl)-1,3-dioxolan-2-yl]phenyl 4-chlorophenyl ether, [2,3-(2,4,4-trimethyltetrahydrofuran)]-1,3-dimethyl-5-chloropyrazole-4carboxanilide [sic], (2,6-dibromo-4-trofluoromethoxy)-2-methyl-4-trifluoromethylthizole-5-carboxanilide [sic], [2-(4xe2x80x2-chlorophenyl)]-2-chloronicotinanilide, N-[(R)-1-(2,4-dichlorophenyl)ethyl]-(S)-2-cyano-3,3-dimethylbutanamide, N-[(R)-1-(4-chlorophenyl)ethyl]-(S)-2,2-cyclopropyl-2xe2x80x2,2-dichloro-3xe2x80x2-methylbutanamide, 3-allyloxy-1,2-benzisothiazole 1,1-dioxide, 2,3-benzisothiadiazole-1-carboxylic acid thioester, 1,2,5,6-tetrahydropyrrolo-[3,2,1-i,j]-quinolin-4-one, 5-methyl-1,2,4-triazolo[3,4-b]benzothiazole, diidopropyl-1,3-dithiolan-2-ylidene [sic] malonate, 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile, N-(i-propoxycarbonyl)-L-valine-(R)-1-(2-napthyl)ethylamide, N-(i-propoxycarbonyl)-L-valine-(R,S)-1-(4-methylphenyl)ethylamide,
strobilurins such as methyl E-methoxyimino-[a-(o-tolyloxy)-o-tolyl]acetate [sic], methyl E-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate, N-methyl-E-methoxyimino-[a-(2-phenoxyphenyl)]acetamide [sic], N-methyl-E-methoxyimino-[a-(2,5-dimethylphenoxy)-o-tolyl]acetamide [sic], methyl (E,E)-methoxy-imino-{2-[1-(3-trifluoromethylphenyl)ethylideneaminooxymethyl]-phenyl}acetate.
In addition, fungicidally active compounds of the formulae I and II may be mentioned from amongst the class of the strobilurins 
in which the substituents have the following meanings:
X is NOCH3, CHOCH3, CHCH3;
Y is O, NH;
Z is oxygen, sulfur, amino (NH);
R1 is hydrogen, cyano, nitro, trifluoromethyl, halogen, C1-C4-alkyl and C1-C4-alkoxy;
m is 0, 1 or 2, it being possible for the radicals R2 to be different if m is 2;
R2 is hydrogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl;
R4 is hydrogen,
C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, it being possible for the hydrocarbon radicals of these groups to be partially or fully halogenated or to have attached to them one to three of the following radicals: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C2-C6-alkenyloxy, C3-C6-cycloalkyl, C3-C6-cycloalkyloxy, heterocyclyl, heterocyclyloxy, aryl, aryloxy, aryl-C1-C4-alkoxy, arylthio, aryl-C1-C4-alkylthio, hetaryl, hetaryloxy, hetaryl-C1-C4-alkoxy, hetarylthio, hetaryl-C1-C4-alkylthio, it being possible for the cyclic radicals, in turn, to be partially or fully halogenated and/or to have attached to them one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio and C(xe2x95x90NOR7)xe2x80x94Anxe2x80x94R8;
C3-C6-cycloalkyl, C3-C6-cycloalkenyl, heterocyclyl, aryl, hetaryl, it being possible for the cyclic radicals to be partially or fully halogenated or to have attached to them one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl and hetaryloxy;
R3, R5 independently of one another are hydrogen,
C1-C10-alkyl, C3-C6-cycloalkyl, C2-C10-alkenyl, C2-C10-alkynyl,
C1-C10-alkylcarbonyl, C2-C10-alkenylcarbonyl, C3-C10-alkynylcarbonyl or C1-C10-alkylsulfonyl, it being possible for these radicals to be partially or fully halogenated or to have attached to them one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, C3-C6-cycloalkyl, C3-C6-cycloalkyloxy, heterocyclyl, heterocyclyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy and hetarylthio, it being possible for the cyclic groups, in turn, to be partially or fully halogenated or to have attached to them one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkyloxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio or C(xe2x95x90NOR7)xe2x80x94Anxe2x80x94R8;
aryl, arylcarbonyl, arylsulfonyl, hetaryl, hetarylcarbonyl or hetarylsulfonyl, it being possible for these radicals to be partially or fully halogenated or to have attached to them one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylcarbonyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3-C6-cycloalkyl,
C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkyloxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl, hetaryloxy or C(xe2x95x90NOR7)xe2x80x94Anxe2x80x94R8;
where
A is oxygen, sulfur or nitrogen and where the nitrogen has attached to it hydrogen or C1-C6-alkyl;
n is 0 or 1;
R7 is hydrogen or C1-C6-alkyl and
R8 is hydrogen or C1-C6-alkyl,
and their salts.
Other structures of the compounds I and II are disclosed in detail in WO 96/32015, pages 3 to 18.
When providing the mixtures, it is preferred to employ the active ingredients of the formula I or II, which may be admixed with other active ingredients against pests (for example insects, arachnids or nematodes) or harmful fungi or else herbicidal or growth-regulatory active ingredients or fertilizers, as required.
They are especially important for controlling a large number of fungi on a variety of crop plants such as cotton, vegetable plants (for example cucumbers, beans and cucurbits), barley, grass, oats, maize, fruiting plants, rice, rye, soybeans, wine, wheat, ornamentals, sugar cane, and a large number of seeds. Specifically, they are suitable for controlling the following plant diseases:
Alternaria species on vegetables and fruit,
Botrytis cinerea (gray mold) on strawberries, vegetables, ornamentals and grapevines,
Cercospora arachidicola on peanuts,
Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,
Erysiphe graminis (powdery mildew) on cereals,
Fusarium and Verticillium species on a variety of plants,
Helminthosporium species on cereals,
Mycosphaerella species on bananas,
Phytophthora infestans on potatoes and tomatoes,
Plasmopara viticola on grapevines,
Podosphaera leucotricha on apples,
Pseudocercosporella herpotrichoides on wheat and barley,
Pseudocercosporella species on hops and cucumbers,
Pseudoperonospora species on hops and cucumbers,
Puccinia species on cereals,
Pyricularia oryzae on rice,
Rhizoctonia species on cotton, rice and turf,
Septoria nodorum on wheat,
Uncinula necator on grapevines,
Ustilago species on cereals and sugar cane, and
Venturia inaequalis (scab) on apples.
Preferred substances amongst the fungicides are systemic strobilurins, which may be employed as a slow-release formulation in rice growing. They should be applied as granules by broadcasting. The dust-free, homogeneous granules should sediment readily in flooded fields or, when flooding treated fields, not rise to the surface, and should be dimensionally stable and storage-stable upon use, even in warmer regions.
The rates of application for the compounds of the formula I, or II, are 2 to 0.01 kg/ha, preferably 0.5 to 0.02 kg/ha, in particular 0.25 to 0.03 kg/ha.
In general, the formulations comprise 0.1 to 80, preferably 0.5 to 40, especially preferably 1 to 20, % by weight of one of the compounds of the formula I or II.
The active ingredients are employed in a purity of 90% to 100%, preferably 95% to 100% (according to 1H NMR or HPLC spectrum [sic]).
The compounds of the formula I or II, their mixtures or the respective formulations are applied by treating the harmful fungi, their environment, or the materials, plants, seeds, soils, areas or spaces to be protected from fungal attack, with a fungicidally active amount of the mixture, or in the case of separate application, of the compounds of the formula I or II. Treatment may be effected before or after attack by the harmful fungi.
Preferred polymeric binders are amorphous and partially crystalline polymers and mixtures of these which can be processed thermoplastically, i.e. as a viscous melt, and which additionally have a solubility in water of less than 100 mg per liter of water at 20xc2x0 C.
Examples of suitable polymeric binders are:
polyolefins such as polyethylene, polypropylene, polybutylene and polyisobutylene; vinyl polymers such as polyvinyl chloride, polyvinyl acetate, polystyrene, polyacrylonitrile, polyacrylates, polymethacrylates; polyacetals such as polyoxymethylene; polyesters such as polyhydroxybutyric acid, polyhydroxyvaleric acid, polyalkylene terephthalates, polyalkylene adipate terephthalates, polybutylene adipate terephthalates; polyester amides; polyether amides; polyamides; polyimides; polyethers; polyether ketones; polyurethanes and polycarbonates. Also copolymers of ethylene/vinyl acetate, ethylene/(meth)acrylates, styrene/acrylonitrile, styrene/butadiene, styrene/butadiene/acrylonitrile, olefin/maleic anhydride.